Manufacture of artificial threads and other products from cellulose compounds



Patented June 11, 1935 7 g v UNITED, STATES PATENT OFFICE MANUFACTURE OFARTIFICIAL THREADS AND OTHER PRODUCTS FROM CELLULOSE COMPOUNDS LeonLilienfeld, Vienna, Austria No Drawing. Application July 14, 1933,Serial No. 680,498. In Great Britain July 15, 1932 7 Claims. (01, 1854)In certain of my copending cases, as noted bechlorohydrine, mannitanechlorohydrine, dulcilow, I have shown, described and claimed proctanmonochlorohydrine, divinyl-ethylene glycol esses of producing artificialmaterials (e. g. chlorohydrine, phenyl propanol chlorohydrine, threads,films, coatings or dressings on textiles, naphthyl propanolchlorohydrine, 4-methoxy paper, etc. and numerous others) by formingnaphthyl propanol chlorohydrine, and the like,

what may be considered to be a solution of a xanas well as the analogousbromine derivatives. ,s I thate of a cellulosic body in which one ormore The halogen derivative selected is added to the of the hydroxylhydrogen atoms has been reviscose andwell mixed therewith, and thesoplaced by organic radicalaandthen coagulating formed solution(optionally after suitable ripen- 111 the latter in a shaped conditioneither by treating) is converted into the proper shape and is 10' ingwith a plasticizing bath (e. g. H2SO4 of at treated with theplasticizing bath,' or with a least'35% and preferably 45% or stronger,orcoagulating bath and then with a plasticizing other acid bath having asimilar strength) or by bath. 1 coagulating said xanthate solution, in ashaped The artificial materials can be desulphurized 1 16, condition,with an acid having merely a coagulat- With NazS solution, orequivalent, preferably with '5 ing actionlesg. a more dilute I-I2S04solution or a warm or hot solution containing at, least 5% other acidsolution or acid salt solution or acid f a2S' 2 s S p being Claimed in y6 and salt solution) and, if desired,-then treating pending applicationSer. No. 464,426, filed June the freshly coagulated artificial materialwith a 2'7, 1930. r a

plasticizing bath (as set forth above). 3 Copending application 20 ThereI are two general methods of preparing filed June 27, 1930, I havedescribed and claimed the solution of xanthates of oxy-organocommodifieetien 0f t above process, in which pounds of cellulose (whichterm will be hereininstead of e halogen d rivativ s of po yhyd afterused, to designate the said xanthate solu- 210011015, tllthlOQELIbOlllCacid esters Of alcohols,

tion, for the sake of brevity), these may be deand p cu y u esters of py y O- 25 scribed briefly. as follows:-(a) Viscose can be hole (6.glycols, glycerine, e c.) a e empleyed made as usual (or according toany known or apfor act g on the viscose. proved formula) and to this canbe added an or- In my impending pp a 597,640 filed ganic materialwhichis capable of reacting there. ch 1932, I have described a further de upon, fication, according to which cellulose xanthate (b) Alkalicellulose, made for example as in the p rably in the form of viscose) istreated usual manner of producing viscose (or in any With One m Organiccompounds of, the typ known or approved manner) is treated with anContaining a polyvaleht aliphatic r anic i organic material capable ofreacting on the celto a least e on a of which Sulphur is lulose contentthereof with substitution of an orattached, and to at least oneotheratom of which 5 ganic radical in place of a hydroxyl hydrogen ahalogen (e. g. chlorine or'bromine) is attached, atom of the cellulose,after which the product is and which organic mp m y r may not treatedwith carbon bisulphide, and the xanalso Contain-One 01' more hydroxyl guc thated productis dissolved in water in the pres- Organic compoundscan be made, for example by ence of alkali I reacting on adichlorohydrine with a solution 4 These methods are described in detailin sevcontautmg. an of N or NaHS less than eral of my other cases, asfonowS: the stoichiometricallyequivalent of the halogen (a) As describedand claimed in Ser. No. element. (chlonne? m h dlhalogenhydnne 435 649filed March 13 1930 to Viscose there is dlchmrohydrme) Thls process anduct are claimed in Ser. No. 597,641. I 45 added alpha dichlorohydrine,the amount of In another co k pending application, Ser. No. wh h m y beequal, to 9% to 9 0f the Welght 618,801 filed June 22, 1932, I havedescribed and O the ee l used m g the 9 claimed a further modificationof the above proc- Instead of a-dlc y ln B7d1chlorohydr1ne, ess in whichcellulose xanthate istreated with '50,- p lo y ethylene chlorohydline,glycone or more organic compounds which contain e inemelloehlorehydrines, viiqllothel halogen an aliphatic polyvalentnucleus, to at least one derivative of a Polyhydric 841001101, such aspinacarbon atom of which is attached a'halogen'elecone chlorohydrine(tetramethyl-ethylene chloment (e. g. chlorine), to another or whichisatrohydrine), ,manmte chlorohydrina. erythrite tached nitrogen such asan NHz group or" NH 5 chlorohydrine or dichlorohydrine,,pentaerythritegroup, and to another of which is attached oxygen such as a hydroxylgroup. Such compounds can be prepared by acting on a dihalogen hy-.drine, such as mchlorohydrine, with ammonia,

preferably at below 100 0., and preferably dissolved in alcohol thisprocess and product being claimed'in my copending application Ser. No.618,800of, June 22, 1932.

. Solutions of xanthates of oxy-organo cellulose compounds can beproduced also, as stated above (b) by acting on alkali cellulose withorganicsubstances as therein defined, (which may be the holagenated orother compounds mentioned above) or by other substances which act in asomewhat analogous manner, then xanthating by treatment with CS2 andthen dissolving the xanthated product in waterand a caustic alkali.Examples of these methods, are given in certain of my other cases as nowto be mentioned.

In my application 435,647, filed March "1930,,

(now Patent 1,858,097) I have described and claimed a process in whichto alkali cellulose (say'a soda cellulose containing 1000 partsof airdrycellulose and 2400 parts of NaGH solution of the making of artificialmaterials by treating such solutions of xanthates of oxy-organocellulose compounds as are produced under Patent 1,858,097, by treatingthe same, in a shaped condition with a plasticizing agent, e. g. H2604of 35%,.preferably 45% or stronger, or other mineralacid of similarstrength. Or, in place of this latter treatment, Icanfirst introduce theshaped xanthate solution into a dilute acid have ing 'merely acoagulating action thereon, and then (if desired) treat the freshlycoagulated material with .an acid solutionhaving a plastioizing actionthereon, such as H2304 of 35% and preferably 45% or stronger.

In Ser. No. 521,017 filed March 7, 1931, I have described andclaimed-the making of artificial materials (including threads) by ap'rocess which diifers from the preceding by the treatment of the alkalicellulose' with an etherifying agent (an alkylating agent, anaralkylating agent or a halogen fatty-acid or salt thereof), thenxanthating the thus obtained product in one of the manners describedabove in connection with Ser. No. 435,647, dissolving in'caustic alkaliand water, shaping the solution of the'xanthate, coagulating andplasti'cizing the product, as described above. 7

=In my Patent 1,910,440, Mayfl23, 1933, I have described and claimedananalegous process in which cellulose, in the presenceof an alkali, isreacted-upon a cyclic ether of the type ethylene oxide, the productxanthated, dissolved in alkali solution-,-and coagulatedanclplasticized.

Many other organicsubstances can likewise reactwith the alkalicellulose, the reaction product xanthated and the x'anthate solutionshaped, oo'agulated and (optionally) plasticized. In my copending case556,719 of August 12, 1931, I have described the employment of. thefollowing,*for thatpurp'ose, the following list:

Di-halogen-zparaffines, for example compounds of the type of ethylenechlorideor tri-methylen'e chloride (which may be regarded as halogenhydracid esters of dihydric parafiln alcohols (glyools) or of the typeof methylene chloride (which may be regarded as neutral halogen hydracidesters of glycols with two hydroxyl groups attached to one and the samecarbon atom).

, Poly-halogen paraflins.

Halogen olefins (halogen substitutidrrfproducts v of unsaturatedhydrocarbons). I

Halogen derivatives of others of mono-hydric alcohols.

Halogen derivatives of aldehydes or ketones. Sulphochlorides of tertiaryamines, such as, for example, the sulphochloride of dimethyl-aniline.Halogen derivatives of higher fatty acids having at least 6 carbonatoms.

Urea halides, alkyl-urea halides, aralkyl-urea halides and aryl-ureahalides.

'Tri-thiocarbonic acid'esters. v 7 Halogen derivatives of cyanogen, suchas cyanogen halides or cyanuric halides (tri -cyano 'gen halidesh' a 3 1Halogen derivatives of di-carboxylic acids, such as halogen succinicacid;

Organic acid esters and inorganic acid esters of -di or polyhydricalcohols (other thanhalogen hydracid esters Some halogen derivatives. ofhydrocarbons of the type CnHzn-tz, for example tri-chlorohydrin1:2:3-tri-chloropropane). Sulphochlorides of hydrocarbons, such. asortho-or 'paratoluene sulphochloride, naphth alene sulpho-chloride.Halogen derivatives of halogenated 7 alkyl phenyl ethers, such asbenzoylated chloro-anisol;

Acid esters of phenols, for example phenyl carbonate or phenyl-ethylcarbonate.

Acid halides, for example benzoyl -"halides,

malonyl halidea'di-ethyl malonyl halides.

hols acids, for example phenyl-halogen-lacticacid orphenyl-halogen-0xy-propionic.acid. Phenyl-acetylene; v 1 Halogenderivatives of olefine-benzols. Halogen derivatives ofphenyl-olefindalcohols or oxy-phenyl-olefine alcohols. Halogenderivatives of .pseudophenols, methylene quinones and quinols, forexample'oritho-oxyf mesityl chloride or piperonyl chloride.

Sulphochlorides of phenyl-monoixy]-carb o i-ry lic acids, such ,assalicylic acid orcresotinic acid; nitro-substitution products and chloroor thereof.

Halogen derivatives of "condensed nuclei, for

ple int-naphthalene-mono halides or halogenatd phthale'nes. I I

1 Halogen derivatives of hydro-naphthalene compounds, for exampledi-hydro-naphthalene- -ell-bromide orvtetra-hydro-naphthalene-glycolchlorhydrin.

Halogen derivatives of heterocyclic compounds having one nitrogen atomin the ring, for ex' i 22,4932, I have described andclaimed theproduction, of, artificial materials from a xanthated solution which hasbeen prepared by acting on alkali cellulose with an organic materialwhich contains hydroxyl attached to at least one carbonatom, andcontains ahalogen element attached to at least one other of thecarbon'atoms thereof :and at' least one sulphur. group (e. g.,SH)attached to still another of the carbon atoms thereof, and the saidcompound of alkali cellulose then'xanthated by CS2, and dissolved.

Also in said application 618,802,-there is described the treatment --ofviscose with a compound of a polyvalent organic radical containing atleast onenitrogen'atom attached to a carbon atom, at least one oxygenatom attached to acarbon atom and at least one acid residue (preferablya halogen atom) attached to a carbon atom: (the; three being preferablyattached to dififerent carbon atoms). Such products can be made byreacting on a dichlorhydrinewith ammonia, at a temperature preferablybelow In all of the abovecases it is to be understood thatthe solutionof a xanthate of an oxy-organo cellulose compound is, after being formedinto the desired shape (e. g. into the shape of a threadlike .stream)treated for being coagulated and plasticiz ed, whereby products (e. g.threads) of high dry and wet tenacity, andhigh (or at least is entirelyfeasible to include both the treatment of the alkali cellulose with theorganic reacting agents above described, and .also the treatment of thexanthate (viscose) therewith, or in other words to add some of theorganic reacting agent (one or a mixture of several) to the alkalicellulose, and to add some more of the same or a different reactingagent (one or a mixture of several) after the xanthation step (andoptionally after the dissolving step).

The said organic reagent, whether added at one or both of the stages ofthe process indicated, may be insufficient to modify all of thecellulose present in the final xanthate solution, so that in such casesthe final solution from which the artificial materials are to beregenerated, will contain some unmodified cellulose xanthate along withone or more xanthates of oxy-organo cellulose compound, whereby uponregeneration there is produced a mixture of cellulose with an oxy-organoderivative of cellulose.

I have now found it is sometimes diflicult to purify the artificialmaterials (including artificial threads) produced as described above,from such xanthates of oxy-organo 1 cellulose-com-. pounds, or' mixturesthereof with viscose, with-. out impairing their extensibility and insomev cases valso'their tensile strength and feel, by any methodsheretoforeknown. The present invention involves a process, one objectofwhich is. to accomplish such purification ,without such: in.-'

juries to the said products. And-the 1117658116111 vention also includesa similar treatmentlof artificial materials produced by coagulating (andoptionally plasticizing) ordinary viscose.

' The present invention is based on the observation that well purifiedproducts having excellent dyeing and other propertiesare obtained whenartificial materials prepared fromthe products which are obtainable bythe above mentioned processes are subjected to desulphuriaation by. thenew process described below. Such newfpro'cess involves the treatment ofthe artificial materials produced as per any of the above mentionedpr'o'c' esses:

(1) with an alkali sulphide solution at a temperature'notexceeding C.and thereafter v (2) with an alkali sulphide solution at a tem-.perature" exceeding 40 0., preferably exceeding 50 C. 1

The process, may be conducted by treatingthe artificial materials, (byimmersion or spraying or any other method known in the desulphuriz'; ingart) for a longer or shorter time withan alkali sulphide solution at atemperaturebelow 25 C., and thereafter the alkalisulphide solutionwithwhich the artificial material inthand is being, treated, is heatedto a temperature ex ceeding 40? C. and kept at that temperature for ashorter or longer time. As an alternative; the artificial material istreated first withan-a-lkali sulphide solution at not above 25- C.and'then with another alkali sulphidesolution of samelor differentstrength which solution has .beenf'p're heated to a temperatureexceeding 410 CI The following examples illustrate" the presentinvention 'which however, is in no waylimited to these examples:

Example 1 I ,7 "A dry or wet skein of artificialsilk produced accordingto one of the processes described in my U. S. applications No. 435,649or Ser. No.

464,427 or Ser. No. 435,648 or Ser. No. 521,017 or Ser. No. 521,018 orSer. No, 556,719 or Ser. No.

597,640 or Ser. No. 618,801 or Ser. No. 618,802 is.

immersed in an aqueous solution of Na2S.9I-I'z0 of per cent. (equal toabout 9.75% actual NazS) strength at 15 C., where, it remains for 10 to20 minutes, whereupon the solution is quickly heated to 100 C., and theskein kept therein for another 10 to 20 minutes at 100 C. After thattime, the skein is removed from the sodium sulphide solution, washedwith hot water, then with cold water and, after having been soured, ifdesired, with dilute sulphuric acid (for example, of 10 per cent.strength), thoroughly washed and dried.

Example 2 A dry or wet skein of artificial silk produced according toone of the processes described in my U. S. applications Ser. No. 435,649or Ser. No.

of 30 per cent. strength at 15 C., where it remains for 10 to 20minutes. Thereupon, the skein is removed from the alkali sulphidesolution and transferred to an alkali sulphide solution'of the samestrength which has been pre-heated to 100 'C. After having remained inthis solution fo'rabout' 10 to 20 minutes, it is washed with" hot water,then with cold'water and, after having been soured, if desired, by meansof dilute sulphuric acid (for example, of 10 per cent. strength), againwashed and dried.

Example 3 The process is conducted 'as in Example 2, but with thedifference that the first alkali sulphide solution contains 43 and thesecond 58 per cent. of'Na S.9HzO. Y I

Example 4 "I'heprocess is conducted asin Example 1, but withthe'difierence that the alkali sulphide solution contains "58 per cent.OfNazSBHz O.v

Example 5 a The process is conducted as in Example 2 but withthedifference that both alkali sulphidesolutions contain 53 percent. ofNazS.9HzO. H

I V Example 6 ""Tl'ieflprocess is conducted as in any one of theExamples 1 to 5, but with the difierence that the temperature used inthe second step is not 1 but 60 C. a

Eiramp le 7 a The process is conducted as in any one of the Examples1,12, 4, and 6, but with the difference that the sodiumsulphide'solu'tion contains only percent. of NazS.9I-IzO (equal to about3.25% actualsNazs). I 1

- Example 8 a "The processis conducted as in Example. 2 or 5, but withthe difference. that thesecond bath 'contains only 10 per cent. ofNazS.9H2O.

v 'I'he'expression cellulosic body" used in th claims is intended toinclude cellulose, cellulose conversion products a and cellulosederivatives capable of being xanthated.

The expression cellulose used in the descrip- V phide.

tionfland claims means, wherever the context permits, cellulose and itsnear .conversionprodoxycellulose. 7

What I claim is: a I

'- 1. Process for vrefining artificial materials; I

made from a solution containing a xanthateof an oxy-organo derivative ofcellulose by wet spinning,'which process comprises treating theiartificial materials first with an alkali sulphide so-' lution ofdesulphurizing'strength, at a temperature not exceeding C. andthereafter withan alkali sulphide solution 'at a temperature exceeding40 C. f :2. A process as claimed in claim L'WheremfbOth treatments areperformed in one and the-@sam'e bath. 3. A process as claimed in claim1, wherein-the treatment isperformed in two separate baths; 4. A processas claimed inclaim 1; wherein thealkali sulphide solution used in bothtreatments contains-not less than per centuof the alkali metal sulphide(figured as crystallized sodium sulphide). I I a 5. A process as claimedin claim '1, wherein the two treatments are carried out with two'sepa-,

contains alkali metal sulphide equivalent to not less than 30 per cent.of crystallized sodium ml:

6. A processes claimed in claim 1, wherein the second treatment isconducted at a temperature not substantiallylower than 100C.

'7; Process for refining artificial materialsat a temperature exceeding50 C., saidsulphide solutions being of a strength suitable fordesulphurizing' said artificial materials r I LEON LILIENFELDQ

